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EP0478154B1 - Verfahren und Mittel zum Einbringen von Gebrauchseigenschaften in einen Körper und der so hergestellte Körper - Google Patents

Verfahren und Mittel zum Einbringen von Gebrauchseigenschaften in einen Körper und der so hergestellte Körper Download PDF

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Publication number
EP0478154B1
EP0478154B1 EP91308013A EP91308013A EP0478154B1 EP 0478154 B1 EP0478154 B1 EP 0478154B1 EP 91308013 A EP91308013 A EP 91308013A EP 91308013 A EP91308013 A EP 91308013A EP 0478154 B1 EP0478154 B1 EP 0478154B1
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EP
European Patent Office
Prior art keywords
silane
article
coating
strength
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP91308013A
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English (en)
French (fr)
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EP0478154A2 (de
EP0478154A3 (en
Inventor
Stephen William Carson
Ryan Richard Dirkx
Victor Dennis Papanu
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Arkema Inc
Original Assignee
Elf Atochem North America Inc
Atochem North America Inc
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Publication date
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Publication of EP0478154A2 publication Critical patent/EP0478154A2/de
Publication of EP0478154A3 publication Critical patent/EP0478154A3/en
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Publication of EP0478154B1 publication Critical patent/EP0478154B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4938—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing silicon bound to hydroxy groups, e.g. trimethyl silanol
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

  • This specification relates to methods for strengthening glass articles and to strengthened glass articles produced by such methods.
  • Glass is intrinsically one of the strongest materials known to man.
  • standard silicate glasses should be able to support stresses as high as 14 to 20 gigapascals (2 to 3 million pounds per square inch [psi]). In practice, however, the strengths typically obtained are on the order of 70 megapascals (MPa), about 10,000 psi.
  • MPa megapascals
  • the explanation of the discrepancy between predicted and measured values is the existence of surface flaws or cracks. These flaws essentially fracture the siloxane network (Si-O-Si), which is the backbone of the glass. This damage to the glass acts to concentrate any applied force, to the extent of causing catastropic failure of the glass article, typically at much lower stresses than otherwise expected. While described here for glass, this same theory can be applied to a wide variety of brittle materials not demonstrating significant plastic deformation prior to failure.
  • the surface flaws or defects can originate from many sources, ranging from unmelted batch materials to scratches produced by sliding across hard surfaces, including other glass articles.
  • the glass articles can be heavily damaged by handling from the moment they are formed. Contact with particulates and moisture in the air, other bottles, guide rails and other handling equipment, and the conveyor on which they are transported, can lead to large decreases in the strength of the container due to the flaws produced.
  • the bottle can be lighter in weight than its untreated counterpart, or be of the same mass while exhibiting generally higher resistance to impact fracture or stress failure.
  • Some approaches to improving the strength of glass include Aratani et al., U.S. 4,859,636, wherein metal ions in the surface of glass are exchanged with ions of a larger radius to develop a surface compressive stress. Poole et al., U.S. 3,743,491, also develop a surface compressive stress, but provide a polymer overcoat to protect the surface from further abrasion.
  • Hashimoto et al., U.S. 4,891,241 treat the surface of the glass with a silane coupling agent followed by a polymer coating containing acryloyl and/or methacryloyl groups, followed by irradiation or thermal treatment to polymerize the molecules containing those groups.
  • US-A-3801361 proposes treating glass articles with an aqueous composition comprising polyethylene in combination with a silane, to provide the articles with a scratch-resistant and lubricious surface.
  • the silane requires a C12 ⁇ 18 alkyl or acyl group.
  • US-A-3873352 is similar, but the silane is an ethylenediaminopropyltrialkoxysilane or polyethyleneiminepropyltrialkoxysilane.
  • a method of increasing the strength of a glass substrate comprising contacting the glass substrate with an aqueous solution of a silane compound selected from vinyl trimethoxysilane methyl trimethoxysilane glycidoxypropyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane methacryloxypropyltrimethoxysilane; and heating and removing water to form a coating.
  • a silane compound selected from vinyl trimethoxysilane methyl trimethoxysilane glycidoxypropyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane methacryloxypropyltrimethoxysilane
  • a strengthened glass article having a coating formed by contacting the article with an aqueous solution made by dissolving a silane compound selected from vinyl trimethoxysilane methyl trimethoxysilane methacryloxypropyltrimethoxysilane; and driving off water to form the coating.
  • a silane compound selected from vinyl trimethoxysilane methyl trimethoxysilane methacryloxypropyltrimethoxysilane
  • Such a silane solution comprises monomers or oligomers containing SiOH groups, as the hydrolysis products of the silanes.
  • the alkoxysilanes are used in concentrations of from about 1wt%, preferably from 5 to 40wt%, most preferably from 7 to 25wt%.
  • the glass substrate may be a silicate glass.
  • the silane solution may be prepared and allowed to stand for a period of time which can range upward from about ten minutes. While not wishing to be bound by theory, it is surmised that this aging period permits the silane molecule to hydrolyze at least partially, to provide SiOH groups which may be transient or in equilibrium with other molecular species in the solution. The SiOH groups can then interact with each other or with groups on the surface of the treated substrate.
  • the aged solution is applied to the surface of the substrate by spraying, brushing, dipping, immersion, or any method which will serve to provide one or a plurality of effective coatings, including, e.g., multiple dipping or spraying.
  • the application can be at any temperature convenient to the particular process; in the case of, e.g., glassware, application of the silane solution is preferably done at the exit, or cold, end of the annealing lehr.
  • the resultant coating is then cured by the any one or a combination of standing at ambient temperature, or the application of energy such as, e.g., IR or UV.
  • the preferred method of curing is by heating the coated article at from about 50 to 250 degrees centigrade.
  • the resulting exterior surface serves as a material which provides the enhancement properties through the composite structure of substrate and coating. If the group is attached to or incorporated into R', that group may be hydrolysed off the parent silane molecule, but will nevertheless be present in the coating applied to the substrate.
  • solution includes chemical solutions, suspensions, emulsions, and mixtures, any of which may exhibit complete or incomplete intermixing.
  • aqueous silane solution is deposited onto the article surface by spraying, dripping, dipping, painting, or any other techniques suited to application of liquids, vapors, or aerosols. After deposition on the surface, what appears to be a condensation reaction leading to the formation of siloxane (Si-O-Si) bonds is induced by, e.g., microwave, IR, or UV irradiation or exposure to ambient or elevated temperatures at, above, or below atmospheric pressure.
  • siloxane (Si-O-Si) bonds is induced by, e.g., microwave, IR, or UV irradiation or exposure to ambient or elevated temperatures at, above, or below atmospheric pressure.
  • silicate materials notably glass
  • the polysiloxane linkage occurs within the coating, as well as between the coating and the surface.
  • the silane coating after bonding to the surface, can act, inter alia, to heal cracks in the surfaces by forming an Si-O-Si network across the flaw surfaces.
  • the formation of the siloxane bonds in the region of the flaws apparently acts to provide an increase in the breaking stress of the article, e.g., a beer bottle or the like. Observed increases in strength by the application of the silane solutions of this invention have been over 350%.
  • the incorporation into the coating on the article of a molecular portion having, e.g. a significant opacity to UV provides protection against degradation of the contents of the bottle.
  • the substrate can be at any temperature above the freezing point of the solution, preferably from about 20 to about 200°C, and most preferably from about 25 to about 130 C.
  • compounds can be added to the silane solution, which compounds are capable of interaction with the silanol group to form a copolymer structure or to form inter-penetrating structures which can be used in conjunction with the silanes.
  • unsaturation and other molecular functionality can be incorporated into the monomeric silane structure, or added to the solution in which the silane is present.
  • Monomers which result in polymeric structures, such as, e.g., amino-formaldehyde, epoxies, and poly-acrylates can be especially useful.
  • soda-lime glass rods are indented with a Vickers diamond to produce approximately 50-micro-meter (um) flaws in the surface. These rod samples are tested in bending and have average strengths of 56 MPa. Samples with identical flaws are spray-coated with a solution of 10 percent by weight (wt.%) of vinyl trimethoxysilane (VTMO) in water. The solution contains enough sulfuric acid to adjust the pH to between 3.0 and 3.4. The samples are thereafter heat-treated for 15 minutes (min.) at 200°C, and tested in bending. The average strength of these samples is found to increase from 56 MPa to 90 MPa.
  • VTMO vinyl trimethoxysilane
  • Example II is a modification of Example I.
  • the samples are again indented rods, and the solution is 10 wt.% VTMO, acidified as set forth in Example I.
  • This solution also contains 0.75 wt.% of a nonionic surfactant. After curing, the indented samples increase in strength from 56 MPa to 93 MPa.
  • Example III is identical to Example I, with the exception that the silane used is methyltrimethoxysilane (MTMO).
  • MTMO methyltrimethoxysilane
  • the control samples have an average strength of 62 MPa. Upon coating and curing, the bend strength increases to 96 MPa.
  • Example IV is a duplication of Example II, using MTMO.
  • the average control strengths are again 62 MPa, but the strengthened samples average 103 MPa.
  • Examples V and VI are duplicates of Examples I and II, respectively, with the exception that the silane used is methacryloxypropyltrimethoxysilane (MPTMO).
  • MPTMO methacryloxypropyltrimethoxysilane
  • the average control strength is 60 MPa.
  • Example V attain an average strength of 126 MPa, while those for Example VI reach 124 MPa.
  • Rectangular bars are cut from a flat disc of Al2O3. Half of the samples as cut are broken by bending by an Instron testing machine with a crosshead speed of 50 millimeters per minute. The average strength of the samples is 23,340 psi, equal to 163 MPa.
  • the balance of the samples are spray-coated with a 10% solution of CETMO containing 0.025 wt.% of a nonionic surfactant and 0.025 wt.% of polyethylene emulsion.
  • the solution is aged for two hours at room temperature prior to its application to the surface of the bar.
  • the samples are thermally cured after spray-coating.
  • the cure is 15 minutes at 125°C followed by 10 min. at 225°C.
  • the average strength of the treated samples is 28,230 psi, or 198 MPa; the increase in strength of the treated material over the untreated samples is 21%.
  • Bottles which have been handled through a sufficient number of normal cleaning and refilling cycles to present a generally scuffed and worn appearance are coated with a silane solution consisting of three silanes in in a solution of 10% total silanes in water.
  • the 1:1:1 solution consists of glycidoxypropyl-trimethoxysilane (GPTMO), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (CETMO), and methyltrimethoxysilane (MTMO).
  • the amount of each silane is about 3.33 wt.%.
  • the solution contains enough sulfuric acid to bring the pH to between 3.0 and 3.4.
  • a nonionic surfactant is added in the amount of 0.75 wt.% in order to increase wetting.
  • the bottles so coated have the visual appearance of bottles which have been through only a minimal number of cleaning and refilling cycles.
  • 2-Hydroxy benzophenone a molecule having the ability to screen UV, is incorporated into a GPTMO molecule. 1.85 grams (g) of that compound are added to 10 g of VTMO in solution, and the solution is allowed to stand at room temperature for 24 hours. The aged material is applied to a sheet of glass by dipping as set forth in Example I. After curing, the samples show a diminution in UV transmission.
  • Example II 2-Hydroxy benzophenone in alcohol solution is added to the solution described with respect to Example I, and the resultant material applied to a sheet of glass as set forth in Example II.
  • the cured samples show substantially the same diminution of transmission of UV radiation as noted in Example IX.
  • Example XI is identical with Example VIII, with the exception that the silane solution used is CETMO further containing a polyethylene emulsion admixed therewith, and the bottles are not subject to repeated cycles of filling and cleaning.
  • the control samples have a slip angle about 30°; the treated bottles have slip angles of about 10°.
  • Samples of poly(methylmethacrylate) sheets are spray-coated with a solution of 10 wt.% of CETMO in water, containing also a polyethylene emulsion admixed therewith.
  • the solution contains enough sulfuric acid to adjust the pH to between 3.0 and 3.4.
  • the samples are thereafter heat-treated for 15 min. at 125°C., and then permitted to cool to room temperature. It is determined that the treated samples have lower friction between treated sheets than between untreated sheets.
  • a colorant comprising FD&C red #40 and FD&C red #3 is added to the coating solution containing the silanes of Example II, and the resulting material used to coat clear bottles by spraying. Upon heat-curing, the bottles have a uniform red coloring. The bottles also exhibit improved burst strength in comparison with control samples.
  • the cure step such methods may be effected by the application of energy of any sort ad magnitude sufficient to remove, e.g., water or other non-coating reaction product from the surface of a treated article, provided that such application is not deleterious to either the glass or the coating material.
  • the curing step being a combined function of energy and time, can include a low magnitude of energy and a relatively long time, or the reverse, an application of energy limited as noted hereinabove, for a relatively short period of time.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Surface Treatment Of Glass (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Silicon Polymers (AREA)
  • Air Bags (AREA)
  • Paints Or Removers (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Laminated Bodies (AREA)
  • Electric Cable Installation (AREA)
  • Control Of Vending Devices And Auxiliary Devices For Vending Devices (AREA)
  • Chemically Coating (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Iron Core Of Rotating Electric Machines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Fats And Perfumes (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Paper (AREA)
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Claims (7)

  1. Verfahren zur Erhöhung der Festigkeit eines Glassubstrats, umfassend das Inkontaktbringen des Glassubstrats mit einer wäßrigen Lösung einer Silanverbindung, ausgewählt aus
       Vinyltrimethoxysilan
       Methyltrimethoxysilan
       Glycidoxypropyltrimethoxysilan
       2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilan
       Methacryloxypropyltrimethoxysilan;
    und das Erhitzen und das Entfernen von Wasser, um einen Überzug herzustellen.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Festigkeit des Glassubstrats durch Bestrahlen des Überzugs mit ultravioletter Strahlung weiter erhöht wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Silan Vinyltrimethoxysilan ist.
  4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Silan Methyltrimethoxysilan ist.
  5. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Silan Methacryloxypropyltrimethoxysilan ist.
  6. Verstärkter Glasgegenstand mit einem Überzug, der hergestellt worden ist durch Inkontaktbringen des Gegenstands mit einer wäßrigen Lösung, hergestellt durch Auflösen einer Silanverbindung, ausgewählt aus
       Vinyltrimethoxysilan
       Methyltrimethoxysilan
       Methacryloxypropyltrimethoxysilan;
    und durch Austreiben des Wassers, um einen Überzug herzustellen.
  7. Verstärkter Glasgegenstand nach Anspruch 6, dadurch gekennzeichnet, daß die Beschichtung mit ultravioletter Strahlung bestrahlt worden ist, um die Festigkeit des Gegenstands weiter zu erhöhen.
EP91308013A 1990-08-30 1991-08-30 Verfahren und Mittel zum Einbringen von Gebrauchseigenschaften in einen Körper und der so hergestellte Körper Expired - Lifetime EP0478154B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US57505290A 1990-08-30 1990-08-30
US575052 1990-08-30
US74417591A 1991-08-13 1991-08-13
US744175 1991-08-13

Publications (3)

Publication Number Publication Date
EP0478154A2 EP0478154A2 (de) 1992-04-01
EP0478154A3 EP0478154A3 (en) 1993-04-14
EP0478154B1 true EP0478154B1 (de) 1995-10-25

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EP91308013A Expired - Lifetime EP0478154B1 (de) 1990-08-30 1991-08-30 Verfahren und Mittel zum Einbringen von Gebrauchseigenschaften in einen Körper und der so hergestellte Körper

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EP (1) EP0478154B1 (de)
JP (1) JPH04231354A (de)
KR (1) KR100213848B1 (de)
CN (1) CN1032967C (de)
AT (1) ATE129488T1 (de)
AU (1) AU647514B2 (de)
BR (1) BR9103731A (de)
CA (1) CA2050110C (de)
CZ (1) CZ266791A3 (de)
DE (1) DE69114097T2 (de)
DK (1) DK0478154T3 (de)
ES (1) ES2080908T3 (de)
GR (1) GR3018556T3 (de)
HU (1) HU210913B (de)
IE (1) IE75704B1 (de)
MX (1) MX9100893A (de)
MY (1) MY110306A (de)
NO (1) NO913342L (de)
NZ (1) NZ239578A (de)
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EP0655953A4 (de) * 1993-06-21 1996-09-04 Atochem North America Elf Spröde oxidsubstrate die durch vernetzte silane verstärkt werden.
US6363749B1 (en) 1997-04-04 2002-04-02 Degussa Ag Process for manufacturing surface-sealed hollow glass containers
US6136382A (en) * 1997-12-29 2000-10-24 Deco Patents, Inc. Method and compositions for decorating vitreous articles with radiation curable inks having improved adhesion and durability
DE19839682A1 (de) 1998-09-01 2000-03-02 Degussa Verfahren zur Herstellung oberflächenversiegelter Hohlglasbehälter mit hoher Gebrauchsfestigkeit
CA2311693A1 (en) 1999-08-10 2001-02-10 Thierry Florent Materne Unsaturated siloxy compounds
FR2872507B1 (fr) * 2004-07-02 2007-05-18 Eurokera Composition de traitement d'une vitroceramique pour en ameliorer la resistance mecanique par guerison des defauts de surface, procedes de traitement correspondants et vitroceramiques traitees obtenues
CN105542521B (zh) * 2016-01-29 2017-08-25 绍兴上虞晶华玻璃有限公司 一种利用废弃玻璃制备复合耐高温涂覆材料的方法
KR102130995B1 (ko) * 2018-12-27 2020-07-09 (주)유티아이 광학 필터용 글라스 기판의 강도 개선 방법 및 이에 의한 강화 글라스 기반 광학 필터

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CZ266791A3 (en) 1993-02-17
SK266791A3 (en) 1995-06-07
MX9100893A (es) 1992-04-01
DE69114097T2 (de) 1996-04-18
AU647514B2 (en) 1994-03-24
BR9103731A (pt) 1992-05-19
CN1032967C (zh) 1996-10-09
NO913342D0 (no) 1991-08-26
HU912827D0 (en) 1992-01-28
AU8272991A (en) 1992-03-05
ATE129488T1 (de) 1995-11-15
EP0478154A2 (de) 1992-04-01
CA2050110A1 (en) 1992-03-01
IE75704B1 (en) 1997-09-10
JPH04231354A (ja) 1992-08-20
KR100213848B1 (ko) 1999-08-02
PL291580A1 (en) 1992-08-24
KR920004147A (ko) 1992-03-27
ES2080908T3 (es) 1996-02-16
IE912980A1 (en) 1992-03-11
MY110306A (en) 1998-04-30
DK0478154T3 (da) 1996-03-18
GR3018556T3 (en) 1996-03-31
DE69114097D1 (de) 1995-11-30
EP0478154A3 (en) 1993-04-14
PL169347B1 (pl) 1996-07-31
CN1061206A (zh) 1992-05-20
NZ239578A (en) 1995-02-24
NO913342L (no) 1992-04-15
PT98836A (pt) 1992-08-31
HU210913B (en) 1995-09-28
HUT61713A (en) 1993-03-01
RU2097349C1 (ru) 1997-11-27
CA2050110C (en) 1997-04-22

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